JP2014504652A - Fusible polyimide molding compound and method for preparing the same - Google Patents

Fusible polyimide molding compound and method for preparing the same Download PDF

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JP2014504652A
JP2014504652A JP2013546562A JP2013546562A JP2014504652A JP 2014504652 A JP2014504652 A JP 2014504652A JP 2013546562 A JP2013546562 A JP 2013546562A JP 2013546562 A JP2013546562 A JP 2013546562A JP 2014504652 A JP2014504652 A JP 2014504652A
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チウ、ズシェウ
ホウ、フェイフェン
バオ、ライヤン
ル、カイ
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    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain

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Abstract

本発明は、可融性ポリイミド成形用コンパウンドの調製方法を提供するものであり、該方法は次の各工程を含む：（工程１）ポリアミド酸溶液の調製：２，３，３’，４’−ＯＤＰＡとオキシジアニリンとを等モル比で非プロトン性極性溶液に投入し、これら両物質を室温で３〜５時間反応させてポリアミド酸溶液を調製し；（工程２）化学イミド化：前記ポリアミド酸溶液１００重量部に対し、脱水剤４０〜１６０重量部、及び第３アミン系有機アルカリ触媒５〜５０重量部を、非極性アレーン等のポリアミド沈殿剤と共に投入し、０．５〜２時間高速撹拌して化学イミド化を完了させ；濾過を経てポリアミド成形用粉末を調製する。ｓ−ポリアミドに比べ、ａ−ポリアミドは成形温度を７０℃下げることができ、２２０℃におけるａ−ポリアミドの機械的性質はｓ−ポリアミドよりも優れ、且つａ−ポリアミドは可溶性及び可融性を有する。  The present invention provides a method for preparing a fusible polyimide molding compound, which includes the following steps: (Step 1) Preparation of a polyamic acid solution: 2, 3, 3 ′, 4 ′ -ODPA and oxydianiline are introduced into an aprotic polar solution at an equimolar ratio, and both substances are reacted at room temperature for 3 to 5 hours to prepare a polyamic acid solution; (Step 2) Chemical imidization: To 100 parts by weight of the polyamic acid solution, 40 to 160 parts by weight of a dehydrating agent and 5 to 50 parts by weight of a tertiary amine organic alkali catalyst are added together with a polyamide precipitating agent such as nonpolar arene, and 0.5 to 2 hours. Stir at high speed to complete chemical imidation; prepare a polyamide molding powder via filtration. Compared to s-polyamide, a-polyamide can lower the molding temperature by 70 ° C, the mechanical properties of a-polyamide at 220 ° C are superior to s-polyamide, and a-polyamide is soluble and fusible. .

Description

本発明は、可融性ポリイミド成形用コンパウンド及びその調製方法に関し、特に２，３，３’，４’−ジフェニルエーテルテトラカルボン酸二無水物とオキシジアニリンとを反応させてａ−ＯＤＰＡ（２，３，３’，４’−ジフェニルエーテルテトラカルボン酸二無水物）／３，４’−ＯＤＡ（３，４’−アミノジフェニルエーテル）成形用粉末を調製する方法に関する。   The present invention relates to a fusible polyimide molding compound and a method for preparing the same, and in particular, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride and oxydianiline are reacted to form a-ODPA (2, 3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride) / 3,4′-ODA (3,4′-aminodiphenyl ether).

ポリイミドは、その優れた耐高温性、耐低温性、耐溶剤性、耐放射線性、並びに顕著な機械的強度及び誘電特性ゆえに注目を集めており、航空宇宙、自動車、マイクロエレクトロニクス、パネル型ディスプレイ等、多くの高度先端技術分野で広く利用されている。１９６０年代にデュポン社がカプトン（Ｋａｐｔｏｎ）フィルム（「カプトン」はイー アイ デュポン ドゥ ヌムール アンド カンパニーの登録商標である。）を開発して以来、約５０年が経過した。ピロメリット酸二無水物（ＰＭＤＡ）とＯＤＡとの線形重合で得られるこのポリイミドは優れた性能を有するが、成形が困難である。つまり、加工成形の難しさ、並びに製造コストの高さの２点がその速やかな発展の妨げとなっていた。ポリイミド材料の加工性を改良し、製造コストを下げる代表的な方法の一つとして、溶融プロセスで製造できる熱可塑性ポリイミドに関する研究開発が挙げられる。溶融プロセスで製造できる熱可塑性ポリイミドは、ポリイミドに関与する当業者らにとって開発目標の一つとなっている。   Polyimides are attracting attention due to their excellent high temperature resistance, low temperature resistance, solvent resistance, radiation resistance, and remarkable mechanical strength and dielectric properties. Aerospace, automobiles, microelectronics, panel type displays, etc. Widely used in many advanced technology fields. About 50 years have passed since DuPont developed Kapton film ("Kapton" is a registered trademark of EI DuPont de Nemours and Company) in the 1960s. This polyimide obtained by linear polymerization of pyromellitic dianhydride (PMDA) and ODA has excellent performance but is difficult to mold. That is, the difficulty of processing and molding and the high manufacturing cost have hindered its rapid development. One of the typical methods for improving the workability of the polyimide material and reducing the production cost is research and development on thermoplastic polyimide that can be produced by a melting process. Thermoplastic polyimides that can be produced by a melt process have become one of the development goals for those skilled in the art involved in polyimides.

３，３’，４，４’−ＯＤＰＡと４，４’−ＯＤＡとの重合反応はジメチルアセトアミド溶媒中で進行し、得られたイミドを粉末化することで可融性ポリイミド成形用粉末（ｓ−ポリイミド）を得ることができる。該ポリマーの繰返しモノマー構造は下記の通り。

上記熱可塑性成形用コンパウンドはＲａｔｅｍＹＳ−２０の商品名で市販されており、１９７０年代に上海市合成樹脂研究所で優れた研究開発が行われていた。この樹脂は、その優れた機械的性質、電気的性質、耐高温性、耐低温性、耐摩耗性ゆえに−２５９〜２２０℃の温度範囲で使用でき、現在では高・低温用シール・ワッシャ、バルブ、ピストン・リング、自動給油軸受及び電気取付部品として用いられている。しかし、上記ｓ−ポリイミドは成形しづらく、通常の成形は３８０℃で圧縮成形にて行われている。近年、省エネルギー、排気ガス低減並びに成形効率の見地から、成形温度を３８０℃から大幅に低下させ、射出成形や押出成形で成形可能とすることが望まれている。 The polymerization reaction of 3,3 ′, 4,4′-ODPA and 4,4′-ODA proceeds in a dimethylacetamide solvent, and the resulting imide is powdered to produce a fusible polyimide molding powder (s -Polyimide) can be obtained. The repeating monomer structure of the polymer is as follows.

The above thermoplastic molding compound is commercially available under the trade name of RateYS-20, and excellent research and development was conducted at the Shanghai Synthetic Resin Research Institute in the 1970s. This resin can be used in the temperature range of -259 to 220 ° C due to its excellent mechanical properties, electrical properties, high temperature resistance, low temperature resistance, and wear resistance, and is currently used for high and low temperature seal washers and valves. , Piston rings, automatic oil supply bearings and electrical mounting parts. However, the s-polyimide is difficult to mold, and normal molding is performed by compression molding at 380 ° C. In recent years, from the viewpoint of energy saving, exhaust gas reduction, and molding efficiency, it has been desired to significantly reduce the molding temperature from 380 ° C. and enable molding by injection molding or extrusion molding.

２１世紀に入ると、日本国宇部興産社と米航空宇宙局（ＮＡＳＡ）が不均一ビフェニルテトラカルボン酸二無水物から成るポリイミド（ＰＩ）について盛んに研究を行い、該ポリマーが４，４’−ＯＤＡよりも高いガラス転移点（Ｔｇ）と優れた加工性を有することを見出した。中国長春応用化学研究所の丁孟賢（Ｄｉｎｇ Ｍｅｎｇｙａｎｇ）の研究チームは、ｓ−ＯＤＰＡの異性体である２，３，３’，４’−ＯＤＰＡと４，４’−ＯＤＡとの反応に関する予備的な研究を牽引した（Ｑ． Ｌｉ，Ｘ． Ｆａｎｇ，Ｚ． Ｗａｎｇ，Ｌ． Ｇａｏ，Ｍ．
Ｄｉｎｇ，Ｊ． Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ，Ｐａｒｔ Ａ： Ｐｏｌｙｍｅｒ Ｃｈｅｍｉｓｔｒｙ， Ｖｏｌ．４１，３２４９，（２００３））。２，３，３’，４’−ＯＤＰＡと４，４’−ＯＤＡとの重合で得られるポリイミドは、下記の構造を有する。:

In the 21st century, Ube Industries, Ltd. and the National Aeronautics and Space Administration (NASA) actively studied polyimide (PI) composed of heterogeneous biphenyltetracarboxylic dianhydride, and the polymer was 4,4'- It has been found that it has a glass transition point (Tg) higher than ODA and excellent workability. Ding Mengyang's research team at Changchun Institute of Applied Chemistry, China, has conducted preliminary research on the reaction of s-ODPA isomers 2,3,3 ', 4'-ODPA with 4,4'-ODA. Led the study (Q. Li, X. Fang, Z. Wang, L. Gao, M .;
Ding, J.A. Polymer Science, Part A: Polymer Chemistry, Vol. 41, 3249, (2003)). A polyimide obtained by polymerization of 2,3,3 ′, 4′-ODPA and 4,4′-ODA has the following structure. :

日本の宇宙科学研究所（ＩＳＡＳ）の横田力男らの研究チーム（Ｙｏｋｏｔａ， Ｐｒｏｃｅｅｄｉｎｇ ｏｆ Ａｉｒｃｒａｆｔ Ｓｙｍｐｏｓｉｕｍ， Ｖｏｌ．４１， Ｎｏ．３， ６０２−６０６（２００３））、及びＮＡＳＡグレン研究センターのＫａｔｈｙ Ｃ． Ｃｈｕａｎｇらの研究チーム（５４ｔｈ Ｉｎｔｅｒｎａｔｉｏｎａｌ ＳＡＭＰＥ Ｓｙｍｐｏｓｉｕｍ， Ｍａｙ １８−２１， Ｂａｌｔｉｍｏｒｅ， ＭＤ（２００９））は、３，３’，４，４’−ＯＤＰＡに代えて２，３，３’，４’−ＯＤＰＡを使用し、レジン・トランスファー・モールディング（ＲＴＭ）用のポリイミド樹脂として利用できるポリイミド、またはフェニルエチニルフタル酸無水物の末端保護型の低分子量プレポリマーを合成した。上記の低分子量ポリマーの主な構造は下記の通り。
Yokota Rikio's research team (Yokota, Proceeding of Aircraft Symposium, Vol. 41, No. 3, 602-606 (2003)) at the Institute for Space Science in Japan (ISAS), and Kathy C. at NASA Glenn Research Center. Chuang et al.'S research team (54th International SAMPE Symposium, May 18-21, Baltimore, MD (2009)) replaced 2,3,3 ', 4'-ODPA instead of 3,3', 4,4'-ODPA. Was used to synthesize a polyimide that can be used as a polyimide resin for resin transfer molding (RTM), or a phenylethynylphthalic anhydride end-protected low molecular weight prepolymer. The main structure of the low molecular weight polymer is as follows.

この他に、横田力男教授らは２，３，３’，４’−ＯＤＰＡと４，４’−オキシジアニリンとからポリイミド薄膜も製造した。この薄膜は、その宇宙環境下での安定性と熱融解性からソーラー・セイルの薄膜材料に用いられる可能性がある。両者を区別するために、この種の構造を有するポリイミドをａ型ポリイミド（以後、ａ−ポリイミドと記載）、３，３’，４，４’−ＯＤＰＡを用いて調製されたポリイミドをｓ型ポリイミド（以後、ｓ−ポリイミドと記載）と称される。   In addition, Prof. Rikio Yokota et al. Produced a polyimide thin film from 2,3,3 ', 4'-ODPA and 4,4'-oxydianiline. This thin film may be used for solar sail thin film materials because of its stability in the space environment and thermal melting properties. In order to distinguish the two, a polyimide having this type of structure is referred to as a-type polyimide (hereinafter referred to as a-polyimide), and polyimide prepared using 3,3 ′, 4,4′-ODPA is referred to as s-type polyimide. (Hereinafter referred to as s-polyimide).

ａ−ポリイミド薄膜の主な性能は下記の通りである。ａ−ポリイミド薄膜のメチルピロリドンへの溶解度は２０％より大きい。上記薄膜に対して３７５℃、２０秒間の熱間プレスを行うと容易に融解し、４５ＭＧｙ及び１００ＭＧｙの陽子線照射下での破断伸度はそれぞれ７３％及び３９％、１ＭＧｙ及び２０ＭＧｙの電子線照射下での破断伸度はそれぞれ６３％及び７６％、照射量１５０ＥＳＤ下での破断伸度は７１％である。上記薄膜は耐放射線性と加工性に優れることから、航空宇宙産業への応用が期待されている。しかしながら、この種の成形用粉末の適当な調製方法はこれまでに知られていない。   The main performance of the a-polyimide thin film is as follows. The solubility of the a-polyimide thin film in methylpyrrolidone is greater than 20%. When the above thin film is hot pressed at 375 ° C. for 20 seconds, it melts easily, and the elongation at break under proton beam irradiation of 45 MGy and 100 MGy is 73% and 39%, respectively, and electron beam irradiation of 1 MGy and 20 MGy, respectively. The breaking elongation at the bottom is 63% and 76%, respectively, and the breaking elongation at an irradiation dose of 150 ESD is 71%. The thin film is excellent in radiation resistance and workability, and is expected to be applied to the aerospace industry. However, no suitable preparation method for this type of molding powder has been known so far.

現状では、ポリイミド成形用粉末の一般的な調製方法として、化学イミド化と熱イミド化とがある。
しかし、成形用粉末の調製に熱イミド化を適用すると、樹脂の劣化、即ち粘度の大幅な低下が生じ、実際、ポリイミド樹脂の粘度低下は最大で、ポリアミド酸の一次粘度の５０％未満にまで低下した。 At present, there are chemical imidization and thermal imidization as general methods for preparing polyimide molding powder.
However, when thermal imidization is applied to the preparation of the molding powder, the resin is deteriorated, that is, the viscosity is greatly reduced. In fact, the polyimide resin has a maximum viscosity reduction of less than 50% of the primary viscosity of the polyamic acid. Declined.

化学イミド化とは、室温で、脱水剤と触媒とをポリアミド酸の溶液系に添加し、高速撹拌しながら所定時間反応させた後、樹脂を液相系から分離回収する。即ち、粘稠溶液系が固液系に変化した後、濾過により粉末を分離回収し、洗浄、乾燥を経て成形に適する粉末、つまり成型用粉末を調製する。上記方法は、生成するポリイミドが溶媒に不溶な系について好適である。勿論、上記粉末は脱水剤と触媒を添加した後に加温することにより調製することもできる。或いは、触媒を添加しないポリアミド酸の溶液系にアレーン系溶媒を添加し、その沸点の高さと容易に水と共沸する性質を利用して、アミン化に伴って生成する水を系外へ除去することができる。生成するポリイミドは、当初のポリアミン酸含有系の溶媒中には溶解しないので、同様に成形用粉末を分離回収することができる。しかしながら、ａ−ＯＤＰＡとジフェニルエーテルジアミンとから合成されるポリイミドは元のポリアミン酸含有系に可溶なので、かかる従来法では調製することができない。ポリイミド溶液を最初に調製し、続いてこのポリイミド溶液を大量のポリイミドの貧溶媒中に分散させる方法も試みられているが、この方法では引火性・可燃性の溶媒を大量に用いる必要があり、生成する粉末の粒径が極めて大きく、調製された粉末が内部に沸点の高い溶媒を含み、この溶媒は蒸発除去することが難しい。また、この粉末は欠陥を生じやすく、得られる成形用粉末の色調は黒色で粒径のバラツキが大きく、凝集しやすく、成型品に気泡を生じやすい。   In chemical imidation, a dehydrating agent and a catalyst are added to a polyamic acid solution system at room temperature, and reacted for a predetermined time while stirring at high speed, and then the resin is separated and recovered from the liquid phase system. That is, after the viscous solution system is changed to a solid-liquid system, the powder is separated and recovered by filtration, and after washing and drying, a powder suitable for molding, that is, a molding powder is prepared. The above method is suitable for a system in which the produced polyimide is insoluble in a solvent. Of course, the powder can also be prepared by heating after adding the dehydrating agent and the catalyst. Alternatively, an arene solvent is added to a polyamic acid solution system to which no catalyst is added, and the water generated by amination is removed out of the system by utilizing its high boiling point and the ability to easily azeotrope with water. can do. Since the produced polyimide does not dissolve in the original polyamic acid-containing solvent, the molding powder can be similarly separated and recovered. However, polyimides synthesized from a-ODPA and diphenyl ether diamine are soluble in the original polyamic acid-containing system and cannot be prepared by such conventional methods. A method of preparing a polyimide solution first and then dispersing this polyimide solution in a large amount of polyimide poor solvent has also been tried, but this method requires the use of a large amount of flammable and flammable solvents, The particle size of the produced powder is extremely large, and the prepared powder contains a solvent having a high boiling point inside, and this solvent is difficult to be removed by evaporation. Further, this powder is liable to cause defects, and the color tone of the obtained molding powder is black and has a large variation in particle diameter, tends to agglomerate, and easily causes bubbles in the molded product.

本発明は、化学イミド化の方法を改良することを目的とし、イミド化プロセスを室温で高速撹拌しながら行うことにより、粒径が細かく均一で、色調が暗くならず、成形が容易な、可溶性かつ可融性のａ−ポリイミド成形用粉末を調製しようとするものである。   The present invention aims to improve the method of chemical imidization, and the imidization process is carried out at room temperature with high-speed stirring, so that the particle size is fine and uniform, the color tone is not dark, and the molding is easy and soluble. In addition, a fusible a-polyimide molding powder is to be prepared.

本発明は、可融性ポリイミド成形用コンパウンドの調製方法を提供することを目的とし、該方法は次の各工程を含む。
（工程１）ポリアミド酸溶液の調製：２，３，３’，４’−ＯＤＰＡとオキシジアニリンとを等モル比で非プロトン性極性溶液に投入し、これら両物質を室温で３〜５時間反応させてポリアミド酸溶液を調製し；
（工程２）化学イミド化：前記ポリアミド酸溶液１００重量部に対し、脱水剤４０〜１６０重量部、及び第３アミン系有機アルカリ触媒５〜５０重量部を、非極性アレーン等のポリアミド沈殿剤と共に投入し、０．５〜２時間高速撹拌して化学イミド化を完了させ；濾過を経てポリアミド成形用粉末を調製する。 An object of the present invention is to provide a method for preparing a fusible polyimide molding compound, and the method includes the following steps.
(Step 1) Preparation of polyamic acid solution: 2,3,3 ′, 4′-ODPA and oxydianiline are charged into an aprotic polar solution at an equimolar ratio, and both these materials are allowed to stand at room temperature for 3 to 5 hours. React to prepare a polyamic acid solution;
(Step 2) Chemical imidization: 40 to 160 parts by weight of a dehydrating agent and 5 to 50 parts by weight of a tertiary amine organic alkali catalyst are added to 100 parts by weight of the polyamic acid solution together with a polyamide precipitating agent such as nonpolar arene. The mixture is stirred at high speed for 0.5 to 2 hours to complete chemical imidation; a polyamide molding powder is prepared through filtration.

前記可融性ポリイミド成形用粉末の調製方法において、前記工程１におけるオキシジアニリンは４，４’−ＯＤＡまたは３，４’−ＯＤＡまたは両者の混合物である。   In the method for preparing a fusible polyimide molding powder, the oxydianiline in Step 1 is 4,4'-ODA or 3,4'-ODA or a mixture of both.

前記可融性ポリイミド成形用粉末の調製方法において、上記非プロトン性極性溶媒はＤＭＡＣ、ＤＭＦ、Ｎ−メチルピロリドン、ＤＭＳＯ及びＧＢＬから選択される１種以上であり、前記非プロトン性極性溶媒の使用量と、 ２，３，３’，４’−ＯＤＰＡ及びＯＤＡの合計使用量との重量比は４〜１０：１である。即ち、ポリアミド酸１ｇを合成するために非プロトン性極性溶媒４〜１０ｇが必要である。   In the method for preparing the fusible polyimide molding powder, the aprotic polar solvent is at least one selected from DMAC, DMF, N-methylpyrrolidone, DMSO and GBL, and the use of the aprotic polar solvent The weight ratio of the amount and the total amount of 2,3,3 ′, 4′-ODPA and ODA used is 4-10: 1. That is, 4-10 g of aprotic polar solvent is required to synthesize 1 g of polyamic acid.

前記可融性ポリイミド成形用粉末の調製方法において、前記工程２で述べた上記非極性アレーンの使用量が前記工程１で述べた非プロトン性極性溶媒の使用量の１０〜５０重量％であり、上記非極性アレーンはトルエンまたはキシレンまたは両者の混合物である。   In the method for preparing the fusible polyimide molding powder, the amount of the nonpolar arene described in Step 2 is 10 to 50% by weight of the amount of the aprotic polar solvent described in Step 1. The nonpolar arene is toluene or xylene or a mixture of both.

前記可融性ポリイミド成形用粉末の調製方法において、前記工程２で述べた脱水剤は無水酢酸、無水プロピオン酸、および両者の混合物から選択される。   In the method for preparing the fusible polyimide molding powder, the dehydrating agent described in Step 2 is selected from acetic anhydride, propionic anhydride, and a mixture of both.

前記可融性ポリイミド成形用粉末の調製方法において、前記工程２で述べた触媒はピリジン、３，５−ルチジン、３−メチルピリジン、４−メチルピリジン、トリメチルアミン、Ｎ−メチルモルホリン、トリエチルアミン及びイソキノリンから選択される１種以上である。   In the method for preparing a fusible polyimide molding powder, the catalyst described in Step 2 is composed of pyridine, 3,5-lutidine, 3-methylpyridine, 4-methylpyridine, trimethylamine, N-methylmorpholine, triethylamine and isoquinoline. One or more selected.

前記可融性ポリイミド成形用粉末の調製方法において、前記工程２は、
前記濾過の後にさらに前記ポリイミド粉末を洗浄、濾別、乾燥する工程を含む。 In the method for preparing the fusible polyimide molding powder, the step 2 includes:
The filtration further includes a step of washing, filtering and drying the polyimide powder.

前記可融性ポリイミド成形用粉末の調製方法において、前記ポリイミド粉末は１００メッシュの標準篩を通過でき、その分子量は数平均分子量で３００００〜３６０００、重量平均分子量で５００００〜７００００、分子量分散度１．９１〜２．００に調節され、好ましくは重量平均分子量を６００００〜７００００とされる。   In the method for preparing the fusible polyimide molding powder, the polyimide powder can pass through a 100-mesh standard sieve, and the molecular weight is 30000-36000 in terms of number average molecular weight, 50000-70000 in terms of weight average molecular weight, and the molecular weight dispersity is 1. The weight average molecular weight is preferably 60000-70000.

前記可融性ポリイミド成形用粉末の調製方法において、前記工程２はさらに、生成したポリイミド粉末に２２０℃〜２８０℃の熱処理を施して成型用粉末のイミド化度を上昇させ、最終的に成形に使用できるポリイミド成形用粉末を調製する工程を含む。   In the method for preparing the fusible polyimide molding powder, the step 2 further includes subjecting the produced polyimide powder to a heat treatment at 220 ° C. to 280 ° C. to increase the imidization degree of the molding powder, and finally to molding. A step of preparing a usable polyimide molding powder.

本発明で提供されるポリイミド成形用粉末は、圧縮成形によりプラスチック試験片に加工することができ、その時の成形温度は２８０〜３５０℃、成形圧力は１５〜７０ＭＰａ、保持時間は被加工物の厚さにもよるが一般に３〜３０分間である。   The polyimide molding powder provided in the present invention can be processed into a plastic test piece by compression molding. At that time, the molding temperature is 280 to 350 ° C., the molding pressure is 15 to 70 MPa, and the holding time is the thickness of the workpiece. Although it depends, it is generally 3 to 30 minutes.

２，３，３’，４’−ａ−ＯＤＰＡとＯＤＡとから構成されるポリイミドの非プロトン性極性溶媒中における溶解度は非常に大きいので、上記粉末は直接的には調製することができず、ゲルが生成してしまう。そこで本発明者らは、上記化学イミド化において上記非プロトン性極性溶媒にトルエン、またはキシレン、または両者の混合物を添加した。この混合溶媒はポリイミド酸を溶解することはできるが、該溶媒中のポリイミドの溶解度を大幅に低下させることができる。   Since the solubility of the polyimide composed of 2,3,3 ′, 4′-a-ODPA and ODA in aprotic polar solvent is very large, the powder cannot be prepared directly, A gel is formed. Therefore, the inventors added toluene, xylene, or a mixture of both to the aprotic polar solvent in the chemical imidation. Although this mixed solvent can dissolve the polyimide acid, the solubility of the polyimide in the solvent can be greatly reduced.

化学イミド化の進行に伴いイミド化度が上昇すると、ポリイミドの溶解度は低下するので、ポリイミドはその溶解度が或るレベルに低下した段階で自然に混合溶媒から分離する。上記非極性アレーン系溶媒はポリイミド酸のみならず、ポリイミドに対しても貧溶媒なので、イミド化プロセス中はポリイミド樹脂溶液系の見かけの粘度を低下させるが、一方で分離したポリイミドに対する該溶液系の溶解力を上昇させることもない。従って、上記ポリイミド成形用粉末は首尾良く分離し、洗浄及び濾過を経て、１００メッシュの標準篩を通過する均一な微粉末を調製することができる。   As the degree of imidization increases with the progress of chemical imidization, the solubility of polyimide decreases, so that the polyimide naturally separates from the mixed solvent when the solubility decreases to a certain level. The non-polar arene solvent is a poor solvent not only for polyimide acid but also for polyimide, so the apparent viscosity of the polyimide resin solution system is reduced during the imidization process, while the solution system for the separated polyimide is It does not increase the dissolving power. Therefore, the above-mentioned polyimide molding powder can be successfully separated, and after washing and filtration, a uniform fine powder passing through a 100 mesh standard sieve can be prepared.

本発明はまた、前記方法により調製される可融性ポリイミド成形用粉末を提供する。ここで、前記ＯＤＰＡとしては３，４’−ＯＤＰＡを選択できる。この場合の上記可融性ポリイミド成形用粉末はａ−ＯＤＰＡ／３，４’−ＯＤＡとなり、成形温度は２９０℃、成形圧力は１５ＭＰａ、ガラス転移温度（ＴＧ）は２５０℃、引張強度（ＭＰａ）は１２０ＭＰａ、引張弾性率（ＧＰａ）は２．５ＭＰａである。ａ−ＯＤＰＡ／４，４’−ＯＤＡ成形用粉末と比較して、ポリイミド成形用粉末ａ−ＯＤＰＡ／３，４’−ＯＤＡはより成形に使い易い。   The present invention also provides a fusible polyimide molding powder prepared by the above method. Here, 3,4PA-ODPA can be selected as the ODPA. In this case, the fusible polyimide molding powder is a-ODPA / 3,4′-ODA, the molding temperature is 290 ° C., the molding pressure is 15 MPa, the glass transition temperature (TG) is 250 ° C., and the tensile strength (MPa). Is 120 MPa, and the tensile modulus (GPa) is 2.5 MPa. Compared with a-ODPA / 4,4'-ODA molding powder, polyimide molding powder a-ODPA / 3,4'-ODA is easier to use for molding.

一方、本発明で調製される可溶性・可融性ポリイミド成形用粉末（ａ−ＯＤＰＡ／４，４’−ＯＤＡ）はＤＭＦ、ＤＭＡＣ、Ｎ−メチルピロリドン、ＤＭＳＯ及びＧＢＬに溶解する。ａ−ＯＤＰＡ／４，４’−ＯＤＡポリイミドの分子量は数平均分子量（Ｍｎ）で３００００〜３６０００、重量平均分子量で５００００〜７００００である。上記ポリイミド成形用粉末のガラス転移温度は２７７〜２８２℃であり、空気中での熱重量分析における５％重量減少温度は５５１℃、１０％重量減少温度は５６７℃、引張強度（ＭＰａ）は１２９ＭＰａ、引張弾性率（ＧＰａ）は２．９６ＧＰａ、圧縮強度は１６０ＭＰａ、圧縮弾性率は１．３９ＧＰａ、曲げ強度は１６８ＭＰ、曲げ弾性率は３．２２ＧＰａ、衝撃強度は２５０ＫＪ／ｍ２又は９４Ｊ／ｍ、及び伸びは２１％である。本発明のａ−ポリイミドとｓ−ポリイミドの機械的性質を下記表１に示す。これらの結果より、ｓ−ポリイミドと比べ、ａ−ポリイミドは高温性能が大幅に改良されていることが解る。 On the other hand, the soluble and fusible polyimide molding powder (a-ODPA / 4,4′-ODA) prepared in the present invention is dissolved in DMF, DMAC, N-methylpyrrolidone, DMSO and GBL. The molecular weight of a-ODPA / 4,4′-ODA polyimide is 30000-36000 in terms of number average molecular weight (Mn) and 50,000-70000 in terms of weight average molecular weight. The polyimide molding powder has a glass transition temperature of 277 to 282 ° C., a 5% weight loss temperature in air thermogravimetric analysis is 551 ° C., a 10% weight reduction temperature is 567 ° C., and a tensile strength (MPa) is 129 MPa. The tensile modulus (GPa) is 2.96 GPa, the compressive strength is 160 MPa, the compressive modulus is 1.39 GPa, the flexural strength is 168 MP, the flexural modulus is 3.22 GPa, the impact strength is 250 KJ / m 2 or 94 J / m, And the elongation is 21%. The mechanical properties of the a-polyimide and s-polyimide of the present invention are shown in Table 1 below. From these results, it can be seen that the high temperature performance of a-polyimide is greatly improved as compared with s-polyimide.


ａ−ＯＤＰＡとＯＤＡとから合成されるポリイミドの溶解度と溶融性を上手く利用し、併せて、成形用粉末の調製において化学イミド化とポリイミド溶液を用いることの利点を活かすことにより、本発明によれば、その初期の段階で高極性の非プロトン性溶媒がポリイミド酸系の形成に用いられ、次に非極性溶媒が添加されて溶媒系の極性が変化し、その一方で、化学イミド化用の触媒が添加されて、可溶性・可融性ポリイミドが調製される。上記調製方法の工程は簡便で、反応条件が穏やかで、操作が簡単かつ安全で、反応効率が高く、従って工業大量生産に適し、生成する成形用粉末は細粒かつ均一で、色調は暗くなりにくく、しかも成形し易い。この他、上記方法により調整されるａ−ポリイミド成形用粉末は既存のｓ−ポリイミド成形用粉末に比べて加工温度が低く、機械的性質に優れ、かつ２２０℃における機械的性質の維持率が高く、極めて広範な用途が見込まれる。
According to the present invention, the solubility and meltability of polyimide synthesized from a-ODPA and ODA can be used well, and the advantages of using chemical imidization and polyimide solution in the preparation of molding powder can be utilized. For example, at the initial stage, a highly polar aprotic solvent is used to form a polyimide acid system, and then a nonpolar solvent is added to change the polarity of the solvent system, while for chemical imidization. A catalyst is added to prepare a soluble and fusible polyimide. The steps of the above preparation method are simple, the reaction conditions are mild, the operation is simple and safe, the reaction efficiency is high, and therefore suitable for industrial mass production, the resulting molding powder is fine and uniform, the color tone becomes dark Difficult and easy to mold. In addition, the a-polyimide molding powder prepared by the above method has a lower processing temperature, superior mechanical properties, and a higher maintenance ratio of mechanical properties at 220 ° C. than the existing s-polyimide molding powders. A very wide range of applications is expected.

以下に具体的な実施形態をまとめ、本発明をさらに説明するが、本発明の権利保護範囲は以下の実施形態に記載される範囲に限定されない。   Specific embodiments will be summarized below and the present invention will be further described. However, the scope of rights protection of the present invention is not limited to the scope described in the following embodiments.

実施形態１
機械式震盪器、温度計及び窒素ガス導入管を備えた５０００ｍｌ容の丸底４ツ口フラスコに、３１０ｇ（１ｍｏｌ）の２，３，３’，４’−ＯＤＰＡ、２００ｇの４，４’−ＯＤＡ、及び２２００ｍｌのＤＭＡＣを投入し、４時間反応させてポリイミド酸溶液を調製し、続いて１０５０ｇの無水酢酸、２６０ｇのトリエチルアミン、及び２２０ｇのトルエンを添加して１時間反応させることによりイミド化を完了させ、ポリイミド粉末を濾別し、続いて該粉末を１０００ｍｌのアセトンで３回洗浄し、濾過後、２時間乾燥させ、２２０〜２８０℃における２〜５時間の熱処理を経て４２６．６ｇのａ−ポリイミド粉末を調製する。収率９０％、数平均分子量（Ｍｎ）＝３３０００、重量平均分子量（Ｍｗ）＝６５０００。上記ポリイミドは、３１０℃／３０ＭＰａの条件で成形してプラスチック試験片とすることができる。このプラスチック試験片の性能指数を表２に示す。
ガラス転移温度：２７７℃
空気中での熱重量分析による５％重量減少温度：５５１℃
空気中での熱重量分析による１０％重量減少温度：５６７℃ Embodiment 1
In a 5000 ml round bottom four-necked flask equipped with a mechanical shaker, thermometer and nitrogen gas inlet tube, 310 g (1 mol) of 2,3,3 ′, 4′-ODPA, 200 g of 4,4′- ODA and 2200 ml of DMAC were added and reacted for 4 hours to prepare a polyimide acid solution. Subsequently, 1050 g of acetic anhydride, 260 g of triethylamine, and 220 g of toluene were added and reacted for 1 hour. Complete, filter the polyimide powder, and then wash the powder three times with 1000 ml of acetone, filter, dry for 2 hours, and heat-treat at 220-280 ° C. for 2-5 hours to 426.6 g of a -Prepare polyimide powder. Yield 90%, number average molecular weight (Mn) = 33000, weight average molecular weight (Mw) = 65000. The polyimide can be molded into a plastic test piece under the condition of 310 ° C./30 MPa. The performance index of this plastic specimen is shown in Table 2.
Glass transition temperature: 277 ° C
5% weight loss temperature by thermogravimetric analysis in air: 551 ° C
10% weight loss temperature by thermogravimetric analysis in air: 567 ° C

比較例１
機械式震盪器、温度計及び窒素ガス導入管を備えた５０００ｍｌ容の丸底４ツ口フラスコに、３１０ｇ（１ｍｏｌ）の２，３，３’，４’−ＯＤＰＡ、２００ｇの４，４’−ＯＤＡ、及び２２００ｍｌのＤＭＡＣを投入し、４時間反応させてポリイミド酸溶液を調製し、続いて１０００ｇの無水酢酸、１３０ｇのトリエチルアミン、及び５００ｇのトルエンを添加して１時間反応させることによりイミド化を完了させ、ポリイミド粉末を濾別し、続いて該粉末を１０００ｍｌのアセトンで３回洗浄し、濾過後、２時間乾燥させ、２２０〜２８０℃における２〜５時間の熱処理を経て４４５．５６ｇのｓ−ポリイミド粉末を調製する。収率９３％、数平均分子量（Ｍｎ）＝３３０００、重量平均分子量（Ｍｗ）＝６５０００。上記ポリイミドは、３８０℃／３０ＭＰａの条件で成形してプラスチック試験片とすることができる。このプラスチック試験片の性能指数を表３に示す。
ガラス転移温度：２６７℃ Comparative Example 1
In a 5000 ml round bottom four-necked flask equipped with a mechanical shaker, thermometer and nitrogen gas inlet tube, 310 g (1 mol) of 2,3,3 ′, 4′-ODPA, 200 g of 4,4′- ODA and 2200 ml of DMAC were added and reacted for 4 hours to prepare a polyimide acid solution. Subsequently, 1000 g of acetic anhydride, 130 g of triethylamine, and 500 g of toluene were added and reacted for 1 hour. Complete, filter the polyimide powder, then wash the powder three times with 1000 ml of acetone, filter, dry for 2 hours, and heat-treat at 220-280 ° C. for 2-5 hours to 445.56 g of s. -Prepare polyimide powder. Yield 93%, number average molecular weight (Mn) = 33000, weight average molecular weight (Mw) = 65000. The polyimide can be molded into a plastic test piece under conditions of 380 ° C./30 MPa. The performance index of this plastic specimen is shown in Table 3.
Glass transition temperature: 267 ° C

前記表２及び表３に示すように、調製したａ−ポリイミドの２２０℃における機械的性質、及び２２０℃における機械的性質の維持率は、比較例１のｓ−ポリイミドよりも良好である。ａ−ポリイミドの成形温度は７０℃低下させることができる。   As shown in Table 2 and Table 3, the mechanical properties of the prepared a-polyimide at 220 ° C. and the maintenance ratio of the mechanical properties at 220 ° C. are better than those of the s-polyimide of Comparative Example 1. The molding temperature of a-polyimide can be lowered by 70 ° C.

実施形態２
脱水剤である無水酢酸の添加量を２５７０ｇとし、トリエチルアミンの添加量を７００ｇとし、キシレンの添加量を２３０ｇとし、イミド化の反応時間を１．５時間とし、アセトンを用いて３回洗浄を行う以外は、実施形態１に記載したと同じ操作及び手順にしたがってポリイミド酸を調製する。ポリイミドの分子量は、Ｍｎ＝３６０００及びＭｗ＝７００００。その他の性能指数は、実施形態１に示したと同じである。 Embodiment 2
The addition amount of acetic anhydride as a dehydrating agent is 2570 g, the addition amount of triethylamine is 700 g, the addition amount of xylene is 230 g, the reaction time of imidization is 1.5 hours, and washing is performed three times with acetone. The polyimide acid is prepared according to the same operation and procedure as described in Embodiment 1 except for the above. The molecular weight of polyimide is Mn = 36000 and Mw = 70000. Other performance indexes are the same as those shown in the first embodiment.

実施形態３
ポリイミド酸の反応時間を５時間とし、無水酢酸の添加量を３６００ｇとし、トリエチルアミンの添加量を２６０ｇとし、キシレンの添加量を１４００ｇとし、イミド化の反応時間を２時間とし、アセトン８００ｇと水２００ｇとの混合液を用いて３回洗浄を行う以外は、実施形態１に記載したと同じ操作及び手順にしたがってポリイミド酸を調製する。ポリイミドの分子量は、Ｍｎ＝３００００及びＭｗ＝５２０００。その他の性能指数は、実施形態１に示したと同じである。 Embodiment 3
The reaction time of polyimide acid was 5 hours, the addition amount of acetic anhydride was 3600 g, the addition amount of triethylamine was 260 g, the addition amount of xylene was 1400 g, the reaction time of imidization was 2 hours, 800 g of acetone and 200 g of water A polyimide acid is prepared in accordance with the same operation and procedure as described in Embodiment 1, except that washing is performed three times using a mixed solution. The molecular weight of polyimide is Mn = 30000 and Mw = 52000. Other performance indexes are the same as those shown in the first embodiment.

実施形態４
４，４’−ＯＤＡに代えて３，４’−ＯＤＡを用いる他は、実施形態１と同様である。ａ−ＯＤＰＡと３，４’−ＯＤＡとから調製されるポリイミドの分子量は、Ｍｎ＝３１０００、Ｍｗ＝５００００、一般構造式は下記の通り。

式中、ｎは６０〜８０の整数である。 Embodiment 4
The third embodiment is the same as the first embodiment except that 3,4′-ODA is used instead of 4,4′-ODA. The molecular weight of polyimide prepared from a-ODPA and 3,4'-ODA is Mn = 31000, Mw = 50000, and the general structural formula is as follows.

In the formula, n is an integer of 60-80.

性能指数は下記の通り。
ａ−ＯＤＰＡ／３，４’−ＯＤＡ
成形圧力：２９０℃／１５ＭＰａ
ガラス転移温度（Ｔｇ）：２５０（℃）
引張強度（ＭＰａ）：１２０ＭＰａ
引張弾性率（ＧＰａ）：２．５ＭＰａ The figure of merit is as follows.
a-ODPA / 3,4'-ODA
Molding pressure: 290 ° C / 15 MPa
Glass transition temperature (Tg): 250 (° C.)
Tensile strength (MPa): 120 MPa
Tensile modulus (GPa): 2.5 MPa

実施形態５
脱水剤である無水酢酸の使用量を１０５０ｇ、トリエチルアミンの使用量を３２０ｇ、ピリジンの使用量を２６０ｇ、キシレンの使用量を２６０ｇとし、イミド化反応時間を１時間とし、アセトンを用いて３回洗浄を行う以外は、実施形態１に記載したと同じ操作及び手順にしたがってポリイミド酸を合成する。ポリイミドの分子量はＭｎ＝３２０００及びＭｗ＝６００００、その他の性能指数は実施形態１で述べたと同様である。 Embodiment 5
The amount of acetic anhydride used as a dehydrating agent is 1050 g, the amount of triethylamine used is 320 g, the amount of pyridine used is 260 g, the amount of xylene used is 260 g, the imidation reaction time is 1 hour, and washing is performed three times with acetone. Except that, polyimide acid is synthesized according to the same operation and procedure as described in the first embodiment. The molecular weight of polyimide is Mn = 32000 and Mw = 60000, and the other figure of merit is the same as described in the first embodiment.

実施形態６
脱水剤である無水酢酸の使用量２５７０ｇ、トリエチルアミンの使用量を３５０ｇ、ピリジンの使用量を３５０ｇ、キシレンの使用量を２５０ｇとし、イミド化反応時間を１．５時間とし、アセトンを用いて３回洗浄を行う以外は、実施形態１に記載したと同じ操作及び手順にしたがってポリイミド酸を合成する。ポリイミドの分子量はＭｎ＝３１０００及びＭｗ＝５５０００、その他の性能指数は実施形態１で述べたと同様である。 Embodiment 6
The amount of acetic anhydride used as a dehydrating agent is 2570 g, the amount of triethylamine used is 350 g, the amount of pyridine used is 350 g, the amount of xylene used is 250 g, the imidation reaction time is 1.5 hours, and acetone is used three times. Except for washing, a polyimide acid is synthesized according to the same operation and procedure as described in the first embodiment. The molecular weight of polyimide is Mn = 31000 and Mw = 55000, and the other figure of merit is the same as described in the first embodiment.

以上、本発明を前記の最良の実施形態にもとづいて説明したが、以上の記載が本発明を限定するものと理解されるべきではない。本明細書の内容を読んだ当業者にとって、本発明の様々な変形や置き換えは自明である。したがって、本発明の範囲は専ら添付の特許請求の範囲により規定されるものである。   As mentioned above, although this invention was demonstrated based on the said best embodiment, the above description should not be understood as limiting this invention. Various modifications and replacements of the present invention will be apparent to those skilled in the art who have read the present description. Accordingly, the scope of the present invention is defined solely by the appended claims.

Claims (10)

次の各工程を含む、可融性ポリイミド成形用粉末の調製方法：
（工程１）ポリアミド酸溶液の調製：２，３，３’，４’−ＯＤＰＡとオキシジアニリンとを等モル比で非プロトン性極性溶液に投入し、これら両物質を室温で３〜５時間反応させてポリアミド酸溶液を調製する；及び
（工程２）化学イミド化：前記ポリアミド酸溶液１００重量部に対し、脱水剤４０〜１６０重量部、及び第３アミン系有機アルカリ触媒５〜５０重量部を、非極性アレーン等のポリアミド沈殿剤と共に投入し、０．５〜２時間高速撹拌して化学イミド化を完了させ；濾過を経てポリアミド成形用粉末を調製する。 Preparation method of fusible polyimide molding powder including the following steps:
(Step 1) Preparation of polyamic acid solution: 2,3,3 ′, 4′-ODPA and oxydianiline are charged into an aprotic polar solution at an equimolar ratio, and both these materials are allowed to stand at room temperature for 3 to 5 hours. (Step 2) Chemical imidization: 40 to 160 parts by weight of a dehydrating agent and 5 to 50 parts by weight of a tertiary amine organic alkali catalyst with respect to 100 parts by weight of the polyamic acid solution. Is added together with a polyamide precipitating agent such as nonpolar arene and stirred at high speed for 0.5 to 2 hours to complete the chemical imidization; a powder for polyamide molding is prepared through filtration. 前記工程１におけるＯＤＡは４，４’−ＯＤＡまたは３，４’−ＯＤＡまたは両者の混合物である、請求項１に記載の可融性ポリアミド成形用粉末の調製方法。 The method for preparing a fusible polyamide molding powder according to claim 1, wherein the ODA in the step 1 is 4,4'-ODA or 3,4'-ODA or a mixture of both. 上記非プロトン性極性溶媒はＤＭＡＣ、ＤＭＦ、Ｎ−メチルピロリドン、ＤＭＳＯ及びＧＢＬから選択される１種以上であり、前記非プロトン性極性溶媒の使用量と、２，３，３’，４’−ＯＤＰＡ及びＯＤＡの合計使用量との重量比は４〜１０：１、即ち、ポリアミド酸１ｇを合成するために非プロトン性極性溶媒４〜１０ｇを必要とする、請求項１または２に記載の可融性ポリイミド成形用粉末の調製方法。 The aprotic polar solvent is at least one selected from DMAC, DMF, N-methylpyrrolidone, DMSO and GBL, and the amount of the aprotic polar solvent used is 2, 3, 3 ′, 4′- The weight ratio of the total amount of ODPA and ODA used is 4 to 10: 1, that is, 4 to 10 g of aprotic polar solvent is required to synthesize 1 g of polyamic acid. Method for preparing fusible polyimide molding powder. 前記工程２で述べた上記非極性アレーンの使用量が前記工程１で述べた非プロトン性極性溶媒の使用量の１０〜５０重量％であり、上記非極性アレーンはトルエンまたはキシレンまたは両者の混合物である、請求項３に記載の可融性ポリイミド成形用粉末の調製方法。 The amount of the nonpolar arene described in Step 2 is 10 to 50% by weight of the amount of the aprotic polar solvent described in Step 1, and the nonpolar arene is toluene or xylene or a mixture of both. A method for preparing a fusible polyimide molding powder according to claim 3. 前記工程２で述べた脱水剤は、無水酢酸、無水プロピオン酸、および両者の混合物から選択される、請求項４に記載の可融性ポリイミド成形用粉末の調製方法。 The method for preparing a fusible polyimide molding powder according to claim 4, wherein the dehydrating agent described in Step 2 is selected from acetic anhydride, propionic anhydride, and a mixture of both. 前記工程２で述べた触媒はピリジン、３，５−ルチジン、３−メチルピリジン、トリメチルアミン、Ｎ−メチルモルホリン、トリエチルアミン及びイソキノリンから選択される１種以上である、請求項１，２，４または５に記載の可融性ポリイミド成形用粉末の調製方法。 The catalyst described in Step 2 is one or more selected from pyridine, 3,5-lutidine, 3-methylpyridine, trimethylamine, N-methylmorpholine, triethylamine, and isoquinoline. A method for preparing the fusible polyimide molding powder described in 1. 前記工程２は、 前記濾過の後にさらに前記ポリイミド粉末を洗浄、濾別、乾燥する工程を含む、請求項１，２，４または５に記載の前記可融性ポリイミド成形用粉末の調製方法。 The said process 2 is a preparation method of the said fusible polyimide molding powder of Claim 1, 2, 4 or 5 which further includes the process of wash | cleaning, filtering and drying the said polyimide powder after the said filtration. 前記ポリイミド粉末は１００メッシュの標準篩を通過でき、その分子量は数平均分子量で３００００〜３６０００、重量平均分子量で５００００〜７００００に調節される、請求項１に記載の前記可融性ポリイミド成形用粉末の調製方法。 The fusible polyimide molding powder according to claim 1, wherein the polyimide powder can pass through a 100-mesh standard sieve, and the molecular weight thereof is adjusted to 30000-36000 in terms of number average molecular weight and 50000-70000 in terms of weight average molecular weight. Preparation method. 前記工程２はさらに、生成したポリイミド粉末に２２０℃〜２８０℃の熱処理を施し、最終的に成形に使用できるポリイミド成形用粉末を調製する工程を含む、請求項１，２，４，５または８に記載の可融性ポリイミド成形用粉末の調製方法。 The step 2 further includes a step of subjecting the produced polyimide powder to a heat treatment at 220 ° C. to 280 ° C. to finally prepare a polyimide molding powder that can be used for molding. A method for preparing the fusible polyimide molding powder described in 1. 前記ＯＤＡは３，４’−ＯＤＡであり、ポリアミドの構造式が下記の通りである、請求項１，５または８に記載の可融性ポリアミド成形用粉末の調製方法：

式中、ｎは６０〜８０の整数である。 The method for preparing a fusible polyamide molding powder according to claim 1, 5 or 8, wherein the ODA is 3,4'-ODA and the structural formula of the polyamide is as follows:

In the formula, n is an integer of 60-80.
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